Manufacture of condensation products from aliphatic aldehydes



Patented 9, 1937 MANUFACTURE OF CONDENSATION PROD- UCTS FROM ALIPHATIC ALDEHYDES Walter Philip Joshua, London, and Herbert MuggletonStanley, Great Bookham, England, Otto Fuchs, Frankfort-on-the-Main, and Wilhelm Querlurth, Mainz-Mombach, Germany, and John BlairDymock, Cheam, England No Drawing. Application March 27, 1934, Serial No. 717,678. In Great Britain October 26, 1931 32 Claims.

This application is a continuation in part of our aggication Serial No. 639,734, filed October 26,

The present invention relates to the manufacture of valuable condensation products from the oxygenated derivatives of the paraffin series of hydrocarbons and specifically relates to the production of alcohols, esters and other valuable derivatives of higher molecular weight from aldehydes such as acetaldehyde or acetaldehyde containing admixtures by catalytic treatment in the presence of hydrogen.

In carrying out the manufacture according to the present invention we use catalysts which consist of a difilcultly reducible oxide or mixture of oxides having only feeble or no basic action and being stable at the prevailing temperature, to-

gether with a metal or mixture of metals known to have a hydrogenating or dehydrogenating actioh and not exceeding in quantity ten per cent by weight of the complete catalyst. The metal or metals may be taken in their metallic state and be admixed as such or the oxide or oxides may be used, it being understood'that' owing to the use of hydrogen as hereinbefore mentioned and as hereinafter described the oxide or oxides will rapidly be reduced. We may also use, as an addition in the catalyst, oxides having a basic reaction,

but we prefer to limit the amount of these basic oxides so that the proportion present is always less than the proportion of the other catalytic constituents. On the other hand we may also employ a catalyst containing larger amounts of the basic oxide. The catalyst may be used on tion are calcium oxide, barium oxide, strontium oxide, magnesia and lithia. By the passage of, a mixture of-acetaldehyde and hydrogen, for instance, over a catalyst consisting of alumina and copper, there may be obtained considerable quantities of higher esters and higher alcohols, and substantially the whole of the acetaldehyde unconverted into the aforesaid higher products is recovered without decomposition.

We have also found that by altering the proportions of metal oxide and catalytic metal in the catalyst, the course of the reaction can be influenced so that either higher yields of al-,

cohols and the like can be produced, or the conversion can be directed towards the production of larger proportions of esters and so forth. It is by-products from a previous process for the procarriers, such as pumice or other inert material.

According to the present invention it is essential that hydrogen should be added to the reaction mixture as it has been found that improved technical results are obtained by this addition;

40 and, moreover, the addition of hydrogen increases duction of higher alcohols, may be used.

The following are examples of the manner in which the invention may be carried into effect and the results obtained. It is understood that these examples are to be considered merely illustrative and are not to be construed in a limiting sense.

Example I The catalyst employed contained in an electrically heated tube of any suitable material such as aluminium was composed as follows:-

drogen to three or more mols hydrogen for each mol. of acetaldehyde.

tures between 150 and 400 C. and moderately in- The conversion can be carried out at temperacreased pressure may be used although we prefer I lytic metals can be mentioned copper, nickel,-

silver, chromium, cadmium. zinc, tin, manganese 55 and'cobalt. Suitable oxides having a basic reac-- I Parts by weight Alumina 100 Calcium oxide Copper and a small amount of ethyl alcohol) were as follows:-

' Parts by weight Butyl actetafe Y 9.3 Butyl butyrate 11.5 Butyl alcohol 20.2 Alcohols higher than butyl alcohol 10.5

Example H The catalyst was composed as follows:-

' Parts by weight Alumina 1 100 Barium oxide 6 Copper 1.5

The treatment being the same as in Example I, the condensation products were as follows:-

Parts by weight Butyl acetate 5.6 Butyl butyrate' 5.3 Butyl alcohol 15.5 Alcohols higher than butyl alcohol 8.3

, Example 111 r The catalyst was composed as follows:

- Parts by weight Alumina 100 Magnesium oxide 6 Copper 1.5

The treatment being the same as in Examples I and II the condensation products were as follows:;

Parts by weight Butyl aceta 6.6 Butylbutyrate 8.6 Butyl alc ol 17.9.. Alcohols higher than butyl-alcohol 10.5

Example IV A catalyst is prepared by impregnation. of activated aluminum oxide with copper formiate in such proportions that there are 95 parts byweight of metallic aluminum for each 5 parts by weight of metaliic'copper. l A mixture 015 1.1 moles of acetaldehyde 1.5 moles of hydrogen is passed thereover in a aluminum tube at 258. The unconsumed acetaldehyde is thereby converted, to an extent of about 40%, into ethyl alcohol. Alter separation of acetaldehyde and ethyl alcohol, there are isolated Parts by weight Butyric aldehyde 35.6 Butanpl I 38 Hexanol fraction (containing about alcohol)- 1.5 High boiling alcohol, etc. (predominately decyl alcohol) 5.0

Example V A catalyst is prepared by impregnation of activated aluminum oxide with copper formiate in such proportions that there are parts by weight of metallic aluminum for each 5 parts by weight of metallic copper. Acetaldehyde together with hydrogerr, in a mole relationship of is passed over this contact 'at 201 or 238. The unconsumed acetaldehyde is thereby partially converted into ethyl alcohol, and as a matter of factJto' a large extent, namely, about 70%, as was to be expected at the low reaction temperature.

' grams of this mixture.

After separation of acetaldehyde and ethyl alco- 1101, the following were found:

Instead of barium oxide, 6 parts by weight of magnesium oxide might be used.

Butyric aldehyde and hydrogen are passed over either of the above contact masses, using about 90 liters of hydrogen for every 100 grs. of aldehyde. Upon treatment of the condensate, the following fractions are obtained:

Grams Ethyl alcohol 27 Ethyl acetate 5.4 Butyric aldehyde 27.5 Butanol 281 Hexanol fraction (contains 20% ester, such as butyl butyrate in addition to aldehydes) Octanol fraction 11.5 High boiling alcohol ester containing 13.0

Example VII The catalyst was composed as follows:

Parts by weight Alumina 100 Barium oxide 6 Copper 1.5

The following mixture in vapor form was passed at 239 C. over the above catalyst:

I, A Parts by weight Acetaldehyde 15 Butyr'ic aldehyde 7.5 Ethyl alnnhnl 73 Water-remainder to make; 100

"70 to 75 liters of hydrogen are used for every Upon treatment of 335 grams of condensate, the following yields are obtained: a

- Grams Acetaldehyde 21.5 'Butyric aldehyde 23 Ethyl alonhnl 114 Ethyl acetate 108 Butanol with some butyl acetate 31 Hexanol fr 12 High boiling alcohols .L L 4 We claim:

1. The process of producing valuable condensation products from aliphatic aldehydes comprising s bjecting "such aliphatic aldehydes in conjunct' n with hydrogen to the action of a mixed catalyst comprising a compound taken from a group consisting of alumina, uranium oxide, thoria, beryllium oxide and zirconium oxide as the preponderant constituent in admixture 76 with a substance taken from a group consisting of copper, nickel, silver, chromium, cadmium, zinc, tin, manganese and cobalt and the oxides thereof, said substance not exceeding in quantity 10% by weight of the ;.complete catalyst and the reaction temperature ranging from about 150 C. to about 400 C.

I 2. The process of producing valuable 'conden sation products from aliphatic aldehydes comprising subjecting such aliphatic aldehydes in conjunction with hydrogen to the action of a mixed catalyst comprising a compound taken mium, cadmium, zinc, tin, manganese and cobalt and the oxides thereof, said substances not ex-- ceeding in quantity 10% ,by weight of the complete catalyst and the reaction temperature ranging from about 150 C. to'about 400 C.

3. The process of producing valuable condensation products from aliphatic aldehydes comprising subjecting such aliphatic aldehydes in conjunction with hydrogen to the action of a mixed catalyst comprising a compound taken from a group consisting of alumina, uranium oxide, thoria, beryllium oxide and zirconium oxide as the preponderant constituent in admixture with a substance taken from a group consisting of copper, nickel, silver, chromium,' cadmium, zinc, tin, manganese and cobalt and the oxides thereof, said substance not exceeding in quantity 10% by weight of the complete catalyst and the reaction temperature ranging from about 150 C. to about 400 C. under superatmospheric pressure.

4. The process of producing valuable conden sation products from aliphatic aldehydes comprising subjecting such aliphatic aldehydes in conjunction with hydrogen to the action of a mixed catalyst comprising a compound taken from a group consisting of alumina, uranium oxide, thoria,, beryllium oxide and zirconium oxide as the preponderant constituent in admixture with a mixture of substances taken from a group consisting of copper, nickel, silver, chromium, cadmium, zinc, tin, manganese and cobalt and the oxides thereof, said substances not exceeding in quantity 10% by weight of the complete catalyst and the reaction temperature ranging from about 150 C. to about 400 C. under superatmospheric pressure.

5. The process of producing valuable condensation products from acetaldehyde comprising subjecting said acetaldehyde in conjunction with hydrogen to the action of a mixed catalyst comprising a compound taken from a group consisting of alumina, uranium oxide, thoria, beryllium oxide and zirconium oxide as the preponderant constituent in admixture with a substance taken from a. group consisting of copper, nickel, silver, chromium, cadmium, zinc, tin, manganese and cobalt and the oxides thereof, said substance not exceeding in quantity 10% by weight of the complete' catalyst and the reaction temperature ranging from about 150 C. to about 400 C. V

- 6. The process of producing valuable condensation products from acetaldehyde comprising subjecting said acetaldehyde in conjunction with hydrogen to the action'of a mixed catalyst comprising a compound taken from a grpup consist ing of alumina, uranium oxide, thoria, beryllium oxide and zirconium oxide as the preponderant constituent in admixture with a mixture of sub- I stances taken from a group consisting of copper, nickel, silver, chromium, cadmium, zinc, tin, manganese and cobalt and the oxides thereof, said substances not exceeding in quantity 10% by weight of the complete catalyst and the reaction temperature ranging from about 150 C. to about 400 C. 1

7. The process of producing valuable condensation products from acetaldehyde comprising subjecting said acetaldehyde in conjunction with hydrogen to the action of a mixed catalyst comprising a compound taken from a group consisting of alumina, uranium oxide, thoria, beryllium oxide and zirconium oxide as the preponderant constituent in admixture with a substance taken from a group consisting of copper, nickel, silver, chromium, cadmium, zinc, tin, manganese and cobalt and the oxides thereof, said substance not exceeding in quantity 10% by weight of the complete catalyst and the reaction temperature ranging from about 150 C. to about 400 C. under superatmospheric pressure.

8. The process of producing valuable condensation products from acetaldehyde comprising subjecting said acetaldehyde in conjunction with hydrogen to the action of a mixed catalyst comprising a compound taken from a group consisting of alumina, uranium oxide, thoria, beryllium oxide and zirconium oxide as the preponderant constituent in admixture with a mixture of 'substances taken from a group consisting of copper, nickel, silver, chromium, cadmium, zinc, tin, manganese and cobalt and the oxides thereof, said substances not exceeding in quantity 10% by weight of the complete catalyst and the reaction temperature ranging from about 150 C. to about 400 C. under superatmospheric pressure.

9. The process of producing valuable condensa-' tion products from aliphatic aldehydes comprising subjecting such aliphatic aldehydes'in conjunction with hydrogen to the action of a mixed catalyst comprising essentially a compound taken from a group consisting of alumina, uranium oxide, thoria, beryllium oxide and zirconium oxide in admixture with a substance taken from a group consisting of copper, nickel, silver, chromioxide, strontium oxide, magnesia and lithia and the reaction temperature ranging from about 150 C. to about 400 C.

' 10. The process of producing valuable condensation products from acetaldehyde comprising I subjecting said acetaldehyde in conjunction with hydrogen to the action of a mixed catalyst comprising essentially a compound taken from a group consisting of alumina, uranium oxide, thoria, beryllium oxide and zirconium oxide in admixture with a substance taken from a group consisting of copper, nickel, silver, chromium," cadmium, zinc, tin, manganese and cobalt and the oxides thereof, said substance not exceeding in quantity 10% by weight of the complete catalyst and in admixture with an agent taken from a group consisting of calcium oxide, barium oxide,

strontium oxide, magnesia and lithia and the reaction temperature ranging from about 150 C. to about 450 C.

11. The process of producing valuable condensation products from aliphatic aldehydes comprising subjecting such alipha'tic aldehydes in conjunction with hydrogen to the action of a taken from a-group consisting of calcium oxide," barium oxide, strontium oxide, magnesia and lithia and the reaction temperature ranging from about 150 C. to about 400 C. and under superatmospheric pressure.

12. The process of producing valuable condensation products from acetaldehyde comprising.

. subjecting said acetaldehyde in conjunction with hydrogen to the action of a mixed catalyst comprising essentially a compound taken from a group consisting of alumina, uranium oxide, thoria, beryllium oxide and zirconium oxidein admixture with a substance taken from a group consisting of copper, nickel, silver, chromium, cadmium, zinc, tin, manganese and cobalt and the oxides there'o'f, said substance not exceeding in quantity 10% by weight of the complete catalyst and in admixture with an agent taken irom'a group consisting of calcium oxide, barium oxide, strontium oxide, magnesia and lithia and the reaction temperature ranging'from about 150 C. to about 400 C. and under superatmospheric pressure.

13. The process of producing valuable condensation products from aliphatic aldehydes comprising subjecting such aliphatic aldehydes in conjunction with hydrogen to the action of a mixed catalyst comprising essentially a compound taken from a group consisting of alumina, uranium oxide, thoria, beryllium oxide and zirconium oxide in admixture with a mixture of substances taken 3 from a group consisting of copper, nickel, silver, chromium, cadmium, zinc, tin, manganese and cobalt and the oxides thereof, said substances not exceeding in quantity 10% by weight of the complete catalyst and in admixture with an agent taken from a groupconsisting of calcium oxide,

barium oxide, strontium oxide, magnesia and lithia and the reaction temperature ranging from about 150? C. to about 400 C.

14. Theprocess of producing valuable condensation products from acetaldehydecomprising admixture with a mixture of substances taken y from a group consisting of coppennickel, silver,

taken'from a group; consisting of calcium oxide, barium oxide. strontium oxide, magnesia and lithia and the reaction temperature ranging from about 150? C. to about 400 C.

15. The process of producing valuable condensation products from aliphatic.aldehydes comprising subjecting such aliphaticaldelrydes in conjunction with hydrogen to the action of a mixed catalyst comprising essentially a compound taken from a group consisting of alumina, uranisilver, chromium, cadmium, zinc, tin, manganese, and cobalt and the oxides thereof, said substances not exceeding in quantity 10% by weight of the complete catalyst and in admixture with an agent taken from a group consisting of calcium omde, barium oxide, strontium oxide, magnesia and lithia and the reaction temperature ranging from about 150 C. to about 400 C. and under superatmospheric pressure.

- 16. The process of producing valuable condensation products from acetaldehyde comprising subjecting said acetaldehyde in conjunction with hydrogen to the action of a mixed catalyst coniprising essentially a compound taken from a group consisting of alumina, uranium oxide, thoria, beryllium oxide and zirconium oxide in admixture with a mixture of substances taken from a group consisting of copper, nickel, silver, chromicadmium zinc; tin, manganese and cobalt and the oxides thereof, said substances not exceeding in quantity 10% by weight of the complete catalyst and in admixture with an agent taken from a group consisting of calcium oxide, barium oxide, strontium oxide, magnesia and lithia and the reaction temperature ranging from about 150 pressure.

1'7. The process of producing valuable condensation products from aliphatic aldehydes comprising subjecting such aliphatic aldehydes in conjunction with hydrogen to the actionof a mixed catalyst comprising essentially a compound taken from a group consisting of alumina, uranium oxide, thoria, beryllium oxide and zirconium oxide in admixture with a substance taken from a group consisting of copper, nickel, silver, chromium, cadmium, zinc, tin, manganese and cobalt and the, oxides thereof, said substance not exceeding in quantity 10% by weight of the complete catalyst and in admixture with magnesia and the reaction temperature ranging from about 150 C. to about 400 C.

18. The process of producing valuable condensation products from acetaldehyde comprising subjecting said acetaldehyde in corriunction with hydrogen to the action of a v ed catalyst comprising essentially a compound ta en from a group consisting of alumina, uranium oxide, thoria, beryllium oxide and zirconium oxide in admixture with a substance taken from a group.

consisting of copper, nickel, silver, chromium cadmium, zinc, tin, manganese and cobalt an the oxides thereof, said substance not excee A in quantity 10% by weight'ofthe complete catalyst and in admixture with magnesia and the reaction temperature ranging from about 150 C. to about 400 C.

19. The process of producing valuable condensation products from aliphatic aldehydes comprising subjecting such aliphatic aldehydes in conjunction with hydrogen to the" action of a mixed catalyst comprising essentially a compound taken from a group consisting of alumina, uranium oxide, thoria, beryllium oxide and zirconium oxide in admixture with a substance taken from a group consisting of copper, nickel, silver, chromium, cadmium, zinc, tin, manganesaand cobalt and the oxides thereof, said substance not exceeding in quantity 10% by weight of the complete catalyst and-in admixture with barium oxide and the reaction temperature'ranging from about 150 C. to about 450 C? 20. The process of producing valuable 0011- I densation products from acetaldehyde comprising, i subjecting said acetaldehyde in commotion with hydrogen to the action oi. a mixed catalyst com-- prising essentially a compound, taken from a group consisting of alumina, uranium oxide, thoria, beryllium oxide and zirconium oxide in admixture with a substance taken from a group consisting of copper, nickel, silver, chromium, cadmium, zinc, tin, manganese and cobalt and the oxides thereof, said substance not exceeding in quantity 10% by weight of the complete catalyst and in admixture with barium oxide and the reaction temperature ranging from about 150 C. to about 450 C. I

21. The process of producing valuable condensation products from alipathic aldehydes comprising-subjecting such aliphatic aldehydes in conjunction with hydrogen to the action of a mixed catalyst comprising essentially a compound taken from a group consisting of alumina, ura nium oxide, thoria, beryllium oxide and zirconium oxide in admixture with a substance taken from a group consisting of. copper, nickel, silver, chromium, cadmium, zinc, tin, manganese and cobalt and the 'oxides thereof, saidsubstance not exceeding in quantity 10% by weight of the complete catalyst and in admixture with calcium oxide and the reaction temperature ranging from about-150 C. to about 450C.

22. The process of producing valuable condensation products from acetaldehyde comprising subjecting said acetaldehyde in conjunction with hydrogen to the action of a mixed catalyst comprising essentially a compound taken from a group consisting of alumina, uranium oxide.

thoria, beryllium oxide and zirconium oxide in admixture with a substance taken from a grgup consisting of copper, nickel, silver, chromium, cadmium, zinc, tin, manganese and cobalt and the oxides thereof, said substance not exceeding in quantity 10% by weight of the complete catalyst and in admixture with calcium oxide and the reaction temperature ranging from about 150 C. to about 450 C. V

23. The process of producing valuable condensation products from aliphatic aldehydes comprising subjecting such aliphatic aldehydes in conjunction with hydrogen to the action 01 a mixed catalyst comprising a dehydrating metal compound which will be stable in the reaction as the preponderant constituent with a. hydrogenating. metal not exceeding in quantity 10% by weight of the complete catalyst, the reaction temperature ranging from about 150 0. to about 450 C. under superatmospheric pressure.

24. The process of producing valuable condensation products from acetaldehyde comprising subjecting said acetaldehyde in conjunction with hydrogen to the action of a mixed catalyst comprising a dehydrating metal compound which will be stable in the reaction as the preponderant constituent with a hydrogenating metal not exceeding in quantity 10% by weight of the complete catalyst, the reaction temperature ranging from about c. to about 450" c. under superatmospheric pressure.

25. A process of producing valuable condensation products from aliphatic aldehydes comprising subjectingsuch aliphatic aldehydes in conjunction with hydrogen to the action of a mixed catalyst comprising essentially alumina in admixture with copper, said copper not exceeding in quantity 10% by weight of the complete catalyst, the reaction temperature ranging from about 150 C. to about 400 C.

26. The process of producing valuable condensation products from acetaldehyde comprising subjecting s'aid acetaldehyde in conjunction with hydrogen to the action of a mixedcatalyst comprising essentially alumina in admixture with copper, said copper not exceeding in quantity 10% by weight of the complete catalyst, the reaction temperature ranging from about 150 Q. to about 400 C.

27. The process of producing valuable condensation products from aliphatic aldehydes comprising subjecting such aliphatic aldehydes in conjunction with hydrogen to the action of a mixed catalyst comprising essentially alumina in admixture with copper and calcium oxide.

28. The process of producing valuable condensation products from acetaldehyde comprising subjecting said acetaldehyde in conjunction with hydrogen to the action of a mixed catalyst comprising essentially alumina in admixture with copper and calcium oxide.

r 29. The process of producing valuable condensation products from aliphatic aldehydes comprising subjecting such aliphatic aldehydes in conjunction with hydrogen to the action of a mixed catalyst comprising essentially alumina in admixture with copper and magnesia.

30. The process of producing valuable condensation products from acetaldehyde comprising subjecting said acetaldehyde in conjunction with hydrogen to the action of a mixed catalyst comprising essentially alumina in admixture with copper and magnesia.

31. The process of producing valuable condensation products from aliphatic aldehydes com.- prising subjecting such aliphatic aldehydes in conjunction with hydrogen to the action of a mixed catalyst comprising essentially alumina in .admixture with copper and bariumpxide. K

32. The process of producing valuable condensation products from, acetaldehyde comprising subjecting said acetaldehyde in conjunction with hydrogen to the action of a mixed catalyst comprising essentially alumina in admixture, with copper and barium oxide.

WALTER PHILIP JOSHUA.

HERBERT MUGGLETON STANLEY.

JOIN BLAIR DYMOCK.

, O'I'IO FUCHS.

WILHEIM QUERFURTH. 

